EP2464693B1 - After clearing agent - Google Patents

After clearing agent Download PDF

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Publication number
EP2464693B1
EP2464693B1 EP10731728.1A EP10731728A EP2464693B1 EP 2464693 B1 EP2464693 B1 EP 2464693B1 EP 10731728 A EP10731728 A EP 10731728A EP 2464693 B1 EP2464693 B1 EP 2464693B1
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EP
European Patent Office
Prior art keywords
polyethyleneimine
component
dyed
weight
composition according
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Revoked
Application number
EP10731728.1A
Other languages
German (de)
French (fr)
Other versions
EP2464693A1 (en
Inventor
Biancamaria Prozzo
Jasmin Kreyer
Stefano Prando
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Huntsman Advanced Materials Switzerland GmbH
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Huntsman Advanced Materials Switzerland GmbH
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Application filed by Huntsman Advanced Materials Switzerland GmbH filed Critical Huntsman Advanced Materials Switzerland GmbH
Priority to EP10731728.1A priority Critical patent/EP2464693B1/en
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Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/52—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing synthetic macromolecular substances
    • D06P1/5264—Macromolecular compounds obtained otherwise than by reactions involving only unsaturated carbon-to-carbon bonds
    • D06P1/5278—Polyamides; Polyimides; Polylactames; Polyalkyleneimines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L39/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Compositions of derivatives of such polymers
    • C08L39/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
    • C08L39/06—Homopolymers or copolymers of N-vinyl-pyrrolidones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/02—Polyamines
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3723—Polyamines or polyalkyleneimines
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/38—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using reactive dyes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/52—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing synthetic macromolecular substances
    • D06P1/5207—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • D06P1/5214—Polymers of unsaturated compounds containing no COOH groups or functional derivatives thereof
    • D06P1/5242—Polymers of unsaturated N-containing compounds
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
    • D06P5/02—After-treatment
    • D06P5/04—After-treatment with organic compounds
    • D06P5/08—After-treatment with organic compounds macromolecular

Definitions

  • the present invention relates to a composition
  • a composition comprising a polymer derived from an N-vinyl heterocycle and a polyethyleneimine and a process for afterclearing a printed or dyed textile material.
  • the dyeing or printing of cellulose fibres with reactive or substantive dyes usually requires repeated rinsing steps using water baths at temperatures up to 98 °C.
  • the part of the dye is removed which is only loosely bound to the surface of the cellulose and which otherwise may cause staining of other fabrics.
  • US Patent No. 6,039,768 describes a process for fixing reactive or substantive dyes on cellulosic fibre material comprising treating the fibre before, during or after dyeing with a liquor containing copolymers of N-vinyl-N-heterocycles, like vinylimidazole/vinylpyrrolidone-copolymers.
  • the fastness properties of the dyeings obtained by this process do not meet the highest requirements.
  • the present invention accordingly relates to a composition
  • a composition comprising
  • Ethylenically unsaturated nitrogen-containing heterocycles suitable for the preparation of the copolymers according to component (a) are, for example, pyrrole, pyrrolidine, pyridine, quinoline, isoquinoline, purine, pyrazole, imidazole, triazole, tetrazole, indolizine, pyridazine, pyrimidine, pyrazine, indole, isoindole, oxazole, oxazolidone, oxazolidine,morpholine, piperazine, piperidine, isoxazole, thiazole, isothiazole, indoxyle, isatine, dioxindole and hydanthoines as well as derivatives thereof.
  • Copolymers suitable as component (a) of the compositions according to the invention can be prepared by polymerising an unsaturated nitrogen-containing heterocycle in the presence of at least one further copolymerisable monomer.
  • a further copolymerisable monomer can be another nitrogen-containing heterocycle or another unsaturated compound like, for instance, vinyl amine, ally amine, acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, vinyl acetate, acrylamide and methacrylamide.
  • the preparation of the polymers can be carried out in a manner known per se, e.g. by ionically or, preferably, radically initiated polymerisation of the corresponding monomers e.g. in solution suspension or emulsion.
  • This polymerisation is preferably carried out in solution with a peroxide, persulfate or an azo compound, like K 2 S 2 O 8 or azo-(bis)-isobutyronitrile, as radical chain starter, which may be present e.g. in an amount of 0.005 to 10 % by weight, based on the monomers used.
  • composition according to the invention contains as component (a) a polymer obtainable by homopolymerisation of N-vinylpyrrolidone or copolymerisation of N-vinylimidazole and N-vinylpyrrolidone.
  • component (a) are polymers, in particular copolymers obtainable by polymerising 60 to 100 mol-%, preferably 70 to 90 mol-%, of N-vinylpyrrolidone and 0 to 40 mol-%, preferably 10 to 30 mol-%, of N-vinylimidazole.
  • the copolymer according to component (a) is typically used in an amount of 0.01 to 4.0 % by weight, preferably of 0.02 to 2.0 % by weight and, particularly preferably, of 0.8 to 2.5 % by weight of active content, based on the weight of the textile material.
  • polyethylenimines suitable as component (b) can likewise be prepared according to known methods.
  • Pure polyethyleneimine (PEI) having a molecular weight M w (weight average) from about 200 g/mol to about 5,000,000 g/mol is generated by acid-catalysed ring-opening polyaddition of the highly reactive aziridine.
  • the branched polymer obtained by this method has primary, secondary and tertiary amino groups and can be modified, for example by reaction with carboxylic acids or carboxylic acid derivatives like chlorides, esters, anhydrides or amides, whereupon partially amidated PEIs are formed.
  • Further modified polyethyleneimines can be prepared by reaction of PEI with alkylene oxides, like ethylene oxide or propylene oxide, thus generating partially ethoxylated or propoxylated polyethyleneimine.
  • Such pure or modified PEIs are commercially available, for example under the designation Lupasol ® (supplied by BASF) or Epomin ® (supplied by Nippon Shokubai).
  • compositions according to the invention contain a modified polyethyleneimine as component (b), in particular a partially amidated or a partially alkoxylated polyethyleneimine.
  • compositions according to the invention contain as component (b) a partially amidated polyethyleneimine obtainable by reaction of a polyethyleneimine with a carboxylic acid, anhydride, ester, chloride or amide.
  • compositions according to the invention contain as component (b) a partially ethoxylated polyethyleneimine obtainable by reaction of a polyethyleneimine with ethylene oxide.
  • the PEI according to component (b) is typically used in an amount of 0.01 to 4.0 % by weight, preferably of 0.05 to 2.0 % by weight and, particularly preferably, of 0.1 to 0.25 % by weight of active content, based on the weight of the textile material.
  • the ratio of the amounts of components (a) and (b) can vary within wide limits.
  • the amount of component (a) is 20 to 80 % by weight, more preferably 30 to 70 % by weight, particularly preferred 40 to 60 % by weight, based on the total weight of components (a) + (b).
  • the amount of component (b) is 20 to 80 % by weight, more preferably 30 to 70 % by weight, particularly preferred 40 to 60 % by weight, based on the total weight of components (a) + (b).
  • a further object of the present invention is a process for afterclearing a printed or dyed textile material, preferably cellulosic textile fibre material, which comprises treating said printed or dyed textile material with an aqueous liquor containing a composition as described above.
  • the process of this invention is preferably carried out by first dyeing the cellulosic fibre material in customary manner and then aftertreating it with a fresh aqueous liquor containing the composition containing components (a) and (b) in the amount indicated above.
  • the dyed cellulosic fibre material can then be dehydrated without any additional rinsing process and dried in customary manner.
  • the cellulosic fibre material may be, for example, regenerated cellulose or, preferably, natural cellulose, typically viscose staple, viscose silk, hemp, linen, jute or, preferably, cotton, and also fibre blends with synthetic fibres, such as cotton/polyamide blends or, preferably, cotton/polyester blends.
  • the textile goods may be used in any form of presentation, e.g. in the form of loose stack consisting completely or partially of native or regenerated cellulose, yarn, cheese, skein, wovens, knitgoods or felt.
  • Dyeings are carried out with substantive or, preferably, reactive dyes, all customary direct and reactive dyes being suitable, such as those described in the Colour Index, 3. Edition (1971) and in the addenda thereto under the headings "Direct Dyes” and "Reactive Dyes”.
  • Typical examples of said dyes are sulfo group-containing monoazo, polyazo, metal complexazo, anthraquinone, phthalocyanine, formazane or dioxazine dyes which, in the case of reactive dyes, carry at least one fibre-reactive group, e.g. a halotriazinyl group or a vinyl sulfonyl radical.
  • the dyeings of the cellulosic fibre material with the dye can be carried out in customary manner by the exhaust process or by a two-step process, for example by padding or printing and subsequent fixation.
  • Dyeing with substantive dyes is preferably carried out by an exhaust process at a neutral to acid pH.
  • Dyeing with reactive dyes is preferably carried out by an exhaust process or by padding with subsequent fixation of the dye on the fibre.
  • Fixation can be effected in customary manner, typically with the action of heat by a steam process or by a thermosol process or, preferably, by a cold pad-batch method, the impregnated fibre material preferably being stored at room temperature.
  • the dyed material is usually rinsed with water at elevated temperature, for example at 40 - 80 °C, preferably at 50 - 70 °C.
  • the aftertreatment is preferably carried out by an exhaust process.
  • the liquor ratio can be chosen from within a wide range and is typically from 1:3 to 1:40 and, preferably, from 1:5 to 1:20.
  • customary dyeing apparatus e.g. open baths, winch becks, jiggers, or paddle jet or circulation apparatus.
  • Processing is conveniently carried out in the temperature range from e.g. 40 to 80°C and, preferably, from 50 to 70°C.
  • the treatment time may typically be from 10 to 100 minutes and, preferably, from 30 to 60 minutes.
  • the pH of the liquor is usually in the range from 8 to 13 and, preferably, from 10 to 12.
  • the liquor can contain other customary additives, typically electrolytes such as sodium chloride or sodium sulfate, dispersants, wetting agents and antifoams.
  • electrolytes typically sodium chloride or sodium sulfate, dispersants, wetting agents and antifoams.
  • the novel process gives dyeings and prints of reactive or substantive dyes on cellulosic fibre material which have an outstanding fastness to wet treatments, such as fastness to washing and water and fastness to chlorine without, however, adversely affecting the colour yield, shade or the light fastness properties.
  • a 10 g piece of a bleached cotton tricot is dyed by exhaust process with a blue reactive dye (Novacron Blue FN-R, supplied by Huntsman) at a liquor ratio of 1:10 (2.0 BZT).
  • the dyed material is taken out of the liquor and rinsed in a water bath for 10 minutes at 60 °C.
  • the fabric is rinsed three times in a water bath, each time for 10 minutes at 60 °C.
  • the product is treated in a rinsing bath containing 0.5 - 2.0 g/l acetic acid at 60 °C for 10 minutes.
  • the residual bath is colourless.
  • a 10 g piece of a bleached cotton tricot is dyed by exhaust process with a blue reactive dye (Novacron Blue FN-R, supplied by Huntsman) at a liquor ratio of 1:10 (2.0 BZT).
  • the dyed material is taken out of the liquor and rinsed in a water bath for 10 minutes at 40 °C.
  • the dyed cotton tricot piece is then treated in a rinsing bath containing 0.5 - 2.0 g/l acetic acid at 70 °C for 10 minutes. Subsequently, it is treated with an aqueous liquor comprising 2 g/l of a commercially available soaping agent (modified poly(acrylic acid)) for 10 minutes at 98 °C.
  • the tricot piece is rinsed in a water bath for 10 minutes at 80 °C, then for 10 minutes at 60 °C and finally for 10 minutes at 40 °C.
  • the residual bath is slightly coloured.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Textile Engineering (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Coloring (AREA)

Description

  • The present invention relates to a composition comprising a polymer derived from an N-vinyl heterocycle and a polyethyleneimine and a process for afterclearing a printed or dyed textile material.
  • The dyeing or printing of cellulose fibres with reactive or substantive dyes usually requires repeated rinsing steps using water baths at temperatures up to 98 °C. Thus, the part of the dye is removed which is only loosely bound to the surface of the cellulose and which otherwise may cause staining of other fabrics.
    For economic and ecological reasons there is a demand for reducing the number of rinsing steps and to decrease the temperature of the rinsing baths.
  • US Patent No. 6,039,768 describes a process for fixing reactive or substantive dyes on cellulosic fibre material comprising treating the fibre before, during or after dyeing with a liquor containing copolymers of N-vinyl-N-heterocycles, like vinylimidazole/vinylpyrrolidone-copolymers. The fastness properties of the dyeings obtained by this process, however, do not meet the highest requirements.
  • It has now been found that the shortcomings mentioned above can be overcome by afterclearing the dyed cellulose fibres with a liquor containing at least one homo- or copolymer of a N-vinyl-N-heterocycle and at least one polyethyleneimine.
  • The present invention accordingly relates to a composition comprising
    1. (a) a copolymer obtainable by polymerisation of at least one ethylenically unsaturated nitrogen-containing heterocyclic compound and
    2. (b) a polyethyleneimine.
  • Ethylenically unsaturated nitrogen-containing heterocycles suitable for the preparation of the copolymers according to component (a) are, for example, pyrrole, pyrrolidine, pyridine, quinoline, isoquinoline, purine, pyrazole, imidazole, triazole, tetrazole, indolizine, pyridazine, pyrimidine, pyrazine, indole, isoindole, oxazole, oxazolidone, oxazolidine,morpholine, piperazine, piperidine, isoxazole, thiazole, isothiazole, indoxyle, isatine, dioxindole and hydanthoines as well as derivatives thereof.
  • Copolymers suitable as component (a) of the compositions according to the invention can be prepared by polymerising an unsaturated nitrogen-containing heterocycle in the presence of at least one further copolymerisable monomer.
    A further copolymerisable monomer can be another nitrogen-containing heterocycle or another unsaturated compound like, for instance, vinyl amine, ally amine, acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, vinyl acetate, acrylamide and methacrylamide.
  • The preparation of the polymers can be carried out in a manner known per se, e.g. by ionically or, preferably, radically initiated polymerisation of the corresponding monomers e.g. in solution suspension or emulsion. This polymerisation is preferably carried out in solution with a peroxide, persulfate or an azo compound, like K2S2O8 or azo-(bis)-isobutyronitrile, as radical chain starter, which may be present e.g. in an amount of 0.005 to 10 % by weight, based on the monomers used.
  • Preferably the composition according to the invention contains as component (a) a polymer obtainable by homopolymerisation of N-vinylpyrrolidone or copolymerisation of N-vinylimidazole and N-vinylpyrrolidone.
  • Especially preferred as component (a) are polymers, in particular copolymers obtainable by polymerising 60 to 100 mol-%, preferably 70 to 90 mol-%, of N-vinylpyrrolidone and 0 to 40 mol-%, preferably 10 to 30 mol-%, of N-vinylimidazole.
  • Independently of the liquor ratio, the copolymer according to component (a) is typically used in an amount of 0.01 to 4.0 % by weight, preferably of 0.02 to 2.0 % by weight and, particularly preferably, of 0.8 to 2.5 % by weight of active content, based on the weight of the textile material.
  • The polyethylenimines suitable as component (b) can likewise be prepared according to known methods.
  • Pure polyethyleneimine (PEI) having a molecular weight Mw (weight average) from about 200 g/mol to about 5,000,000 g/mol is generated by acid-catalysed ring-opening polyaddition of the highly reactive aziridine.
    The branched polymer obtained by this method has primary, secondary and tertiary amino groups and can be modified, for example by reaction with carboxylic acids or carboxylic acid derivatives like chlorides, esters, anhydrides or amides, whereupon partially amidated PEIs are formed.
    Further modified polyethyleneimines can be prepared by reaction of PEI with alkylene oxides, like ethylene oxide or propylene oxide, thus generating partially ethoxylated or propoxylated polyethyleneimine.
    Such pure or modified PEIs are commercially available, for example under the designation Lupasol® (supplied by BASF) or Epomin® (supplied by Nippon Shokubai).
  • Preferably the compositions according to the invention contain a modified polyethyleneimine as component (b), in particular a partially amidated or a partially alkoxylated polyethyleneimine.
  • In a further preferred embodiment, the compositions according to the invention contain as component (b) a partially amidated polyethyleneimine obtainable by reaction of a polyethyleneimine with a carboxylic acid, anhydride, ester, chloride or amide.
  • In a further preferred embodiment, the compositions according to the invention contain as component (b) a partially ethoxylated polyethyleneimine obtainable by reaction of a polyethyleneimine with ethylene oxide.
  • Independently of the liquor ratio, the PEI according to component (b) is typically used in an amount of 0.01 to 4.0 % by weight, preferably of 0.05 to 2.0 % by weight and, particularly preferably, of 0.1 to 0.25 % by weight of active content, based on the weight of the textile material.
  • The ratio of the amounts of components (a) and (b) can vary within wide limits.
    Preferably the amount of component (a) is 20 to 80 % by weight, more preferably 30 to 70 % by weight, particularly preferred 40 to 60 % by weight, based on the total weight of components (a) + (b).
  • Correspondingly, the amount of component (b) is 20 to 80 % by weight, more preferably 30 to 70 % by weight, particularly preferred 40 to 60 % by weight, based on the total weight of components (a) + (b).
  • A further object of the present invention is a process for afterclearing a printed or dyed textile material, preferably cellulosic textile fibre material, which comprises treating said printed or dyed textile material with an aqueous liquor containing a composition as described above.
  • The process of this invention is preferably carried out by first dyeing the cellulosic fibre material in customary manner and then aftertreating it with a fresh aqueous liquor containing the composition containing components (a) and (b) in the amount indicated above. The dyed cellulosic fibre material can then be dehydrated without any additional rinsing process and dried in customary manner.
  • The cellulosic fibre material may be, for example, regenerated cellulose or, preferably, natural cellulose, typically viscose staple, viscose silk, hemp, linen, jute or, preferably, cotton, and also fibre blends with synthetic fibres, such as cotton/polyamide blends or, preferably, cotton/polyester blends.
  • The textile goods may be used in any form of presentation, e.g. in the form of loose stack consisting completely or partially of native or regenerated cellulose, yarn, cheese, skein, wovens, knitgoods or felt.
  • Dyeings are carried out with substantive or, preferably, reactive dyes, all customary direct and reactive dyes being suitable, such as those described in the Colour Index, 3. Edition (1971) and in the addenda thereto under the headings "Direct Dyes" and "Reactive Dyes".
  • Typical examples of said dyes are sulfo group-containing monoazo, polyazo, metal complexazo, anthraquinone, phthalocyanine, formazane or dioxazine dyes which, in the case of reactive dyes, carry at least one fibre-reactive group, e.g. a halotriazinyl group or a vinyl sulfonyl radical.
  • The dyeings of the cellulosic fibre material with the dye can be carried out in customary manner by the exhaust process or by a two-step process, for example by padding or printing and subsequent fixation.
  • Dyeing with substantive dyes is preferably carried out by an exhaust process at a neutral to acid pH.
  • Dyeing with reactive dyes is preferably carried out by an exhaust process or by padding with subsequent fixation of the dye on the fibre. Fixation can be effected in customary manner, typically with the action of heat by a steam process or by a thermosol process or, preferably, by a cold pad-batch method, the impregnated fibre material preferably being stored at room temperature.
    Subsequently the dyed material is usually rinsed with water at elevated temperature, for example at 40 - 80 °C, preferably at 50 - 70 °C.
  • The aftertreatment is preferably carried out by an exhaust process. The liquor ratio can be chosen from within a wide range and is typically from 1:3 to 1:40 and, preferably, from 1:5 to 1:20.
  • Special appliances are not required. It is possible to use, for example, the customary dyeing apparatus, e.g. open baths, winch becks, jiggers, or paddle jet or circulation apparatus.
  • Processing is conveniently carried out in the temperature range from e.g. 40 to 80°C and, preferably, from 50 to 70°C. The treatment time may typically be from 10 to 100 minutes and, preferably, from 30 to 60 minutes. The pH of the liquor is usually in the range from 8 to 13 and, preferably, from 10 to 12.
  • In addition to the composition containing components (a) and (b), the liquor can contain other customary additives, typically electrolytes such as sodium chloride or sodium sulfate, dispersants, wetting agents and antifoams.
  • The novel process gives dyeings and prints of reactive or substantive dyes on cellulosic fibre material which have an outstanding fastness to wet treatments, such as fastness to washing and water and fastness to chlorine without, however, adversely affecting the colour yield, shade or the light fastness properties.
  • While respective customary aftertreatment processes are carried out almost at boiling temperature, moderate temperatures (60 - 80 °C) are adequate for successfully conducting the afterclearing process according to the invention.
  • Furthermore, the number of rinsing steps can be reduced in comparison to conventional prior art methods.
  • The following Examples illustrate the invention in more detail.
    • Example 1
  • A 10 g piece of a bleached cotton tricot is dyed by exhaust process with a blue reactive dye (Novacron Blue FN-R, supplied by Huntsman) at a liquor ratio of 1:10 (2.0 BZT). The dyed material is taken out of the liquor and rinsed in a water bath for 10 minutes at 60 °C.
    The dyed cotton tricot piece is then treated for 10 minutes at 60 °C with a fresh aqueous liquor comprising 2 g/l of an aqueous solution containing 10 % by weight of a N-vinylimidazole/N-vinylpyrrolidone-copolymer, prepared from 20 mol-% of N-vinylimidazole and 80 mol-% of N-vinylpyrrolidone, and 0.5 g/l of an aqueous solution containing 50 % by weight of a modified branched PEI having a molecular weight (weight average) Mw = 750,000 g/mol, pH = 11. Subsequently, the fabric is rinsed three times in a water bath, each time for 10 minutes at 60 °C. Finally, the product is treated in a rinsing bath containing 0.5 - 2.0 g/l acetic acid at 60 °C for 10 minutes. The residual bath is colourless.
    • Example 2 (Comparison)
  • A 10 g piece of a bleached cotton tricot is dyed by exhaust process with a blue reactive dye (Novacron Blue FN-R, supplied by Huntsman) at a liquor ratio of 1:10 (2.0 BZT). The dyed material is taken out of the liquor and rinsed in a water bath for 10 minutes at 40 °C.
    The dyed cotton tricot piece is then treated in a rinsing bath containing 0.5 - 2.0 g/l acetic acid at 70 °C for 10 minutes. Subsequently, it is treated with an aqueous liquor comprising 2 g/l of a commercially available soaping agent (modified poly(acrylic acid)) for 10 minutes at 98 °C. Afterwards, the tricot piece is rinsed in a water bath for 10 minutes at 80 °C, then for 10 minutes at 60 °C and finally for 10 minutes at 40 °C. The residual bath is slightly coloured.
  • The dyed specimens are tested according to standard methods (ISO 105 E01) with respect to several fastness properties. The results are summarised in Table 1. Table 1:
    Example 1 (invention) Example 2 (comparison)
    Fastness to washing 3 3
    Fastness to water (severe) 4 3
    Fastness to rubbing 3 3
    Fastness to light 3 3
    Fastness to perspiration (alkali) 4 3
    Fastness to perspiration (acid) 4 3

Claims (9)

  1. A composition comprising
    (a) a N-vinylimidazole/N-vinylpyrrolidone-copolymer and
    (b) a polyethyleneimine.
  2. A composition according to claim 1 comprising as component (b) a modified polyethyleneimine.
  3. A composition according to claim 2 comprising as component (b) a partially amidated or a partially alkoxylated polyethyleneimine.
  4. A composition according to claim 2 comprising as component (b) a partially amidated polyethyleneimine obtainable by reaction of a polyethyleneimine with a carboxylic acid, anhydride, ester, chloride or amide.
  5. A composition according to claim 3 comprising as component (b) a partially ethoxylated polyethyleneimine obtainable by reaction of a polyethyleneimine with ethylene oxide.
  6. A process for afterclearing a printed or dyed textile material which comprises treating said printed or dyed textile material with an aqueous liquor containing a composition according to any one of claims 1 to 5.
  7. A process according to claim 6, wherein the temperature of the aqueous liquor is 50-70 °C.
  8. A process according to claims 6 or 7, wherein the pH value of the aqueous liquor is 10-12.
  9. A process according to any one of claims 6 to 8, wherein said textile material is printed or dyed with reactive dyes.
EP10731728.1A 2009-08-13 2010-07-06 After clearing agent Revoked EP2464693B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP10731728.1A EP2464693B1 (en) 2009-08-13 2010-07-06 After clearing agent

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EP09167829 2009-08-13
EP10731728.1A EP2464693B1 (en) 2009-08-13 2010-07-06 After clearing agent
PCT/EP2010/059643 WO2011018279A1 (en) 2009-08-13 2010-07-06 Afterclearing agents

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EP2464693A1 EP2464693A1 (en) 2012-06-20
EP2464693B1 true EP2464693B1 (en) 2015-01-28

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KR (1) KR20120089456A (en)
CN (1) CN102471591B (en)
BR (1) BR112012003115A2 (en)
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WO (1) WO2011018279A1 (en)

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US9873798B2 (en) 2014-02-25 2018-01-23 General Electric Company Composition and method for use in three dimensional printing
CN112726236B (en) * 2020-12-28 2022-06-17 绍兴海成化工有限公司 Neutralization soaping agent

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4548744A (en) * 1983-07-22 1985-10-22 Connor Daniel S Ethoxylated amine oxides having clay soil removal/anti-redeposition properties useful in detergent compositions
GB8609704D0 (en) * 1986-04-21 1986-05-29 Ici Plc Coating composition
US5277812A (en) 1993-02-12 1994-01-11 Gelman Sciences Inc. Inter-penetrating network charge modified microporous membrane
US5698476A (en) * 1995-03-01 1997-12-16 The Clorox Company Laundry article for preventing dye carry-over and indicator therefor
WO1997035067A1 (en) * 1996-03-21 1997-09-25 Betzdearborn Inc. Antifoam compositions containing polymers and methods of use thereof
EP0812949A3 (en) 1996-06-11 1998-07-22 Ciba SC Holding AG Process for the treatment of dyed fibrous cellulosic materials
EP0918089A1 (en) * 1997-11-24 1999-05-26 The Procter & Gamble Company Fabric care compositions
US6410503B1 (en) * 1997-11-24 2002-06-25 The Procter & Gamble Company Fabric care compositions
GB0005089D0 (en) * 2000-03-01 2000-04-26 Unilever Plc Bleaching and dye transfer inhibiting composition and method for laundry fabrics
GB0005090D0 (en) * 2000-03-01 2000-04-26 Unilever Plc Bleaching and dye transfer inhibiting composition and method for laundry fabrics
DE10027634A1 (en) * 2000-06-06 2001-12-13 Basf Ag Use of hydrophobic polymer particles, cationically modified by coating with cationic polymer, as additives in washing or care materials for textiles and as additives in detergents
DE10124387A1 (en) * 2001-05-18 2002-11-28 Basf Ag Hydrophobically modified polyethyleneimine and polyvinylamine as anticrease agents for treatment of cellulose containing textiles, useful as textile finishing agents in both solid and liquid formulations
US20050112151A1 (en) * 2003-11-20 2005-05-26 Horng Liou L. Skin adherent hydrogels
US20080005852A1 (en) * 2004-07-27 2008-01-10 Nano-Tex, Inc. Durable multifunctional finishing of fabrics

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Publication number Publication date
PT2464693E (en) 2015-05-25
CN102471591B (en) 2015-02-11
US20120129754A1 (en) 2012-05-24
KR20120089456A (en) 2012-08-10
CN102471591A (en) 2012-05-23
WO2011018279A1 (en) 2011-02-17
US8740992B2 (en) 2014-06-03
BR112012003115A2 (en) 2016-02-23
EP2464693A1 (en) 2012-06-20

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